Silver halide emulsion containing acylamidophenol photographic couplers

ABSTRACT

Cyan dye-forming phenolic or Alpha -naphtholic coupler compounds having a p-hydroxy-alkylphenoxy-alkylcarbonamido substituent in a non-coupling ring position thereon; a silver halide emulsion containing at least one of such coupler; a color photographic element comprising a support and at least one silver halide emulsion containing the above coupler applied thereto; and a method for preparing a cyan photographic dye by reacting one of the above defined couplers with oxidized color developing agent.

United States Patent Lau et a1. Apr. 29, 1975 [54] SILVER I'IALIDE EMULSION CONTAINING 2,330,291 9/1943 Kirby 96/100 ACYLAMIDOPHENOL PHOTOGRAPH: 2,357,394 9/1944 Frohlich et a1. 96/100 3,519,429 7/1970 Lcstina 96/100 COUPLERS 3,758,308 9/1973 Beavers et a1. 96/100 [75] Inventors; Philip T. Lau; Ilmari F, Salminen; 3,779,763 12/1973 Lau 96/100 Leo E. Beavers, all of Rochester, Primary Examiner-J. Travis Brown [73] Assignee: Eastman Kodak Company, Attorney, g J- T- e is Rochester, N.Y.

[22] Filed: Oct. 1, 1973 57 ABSTRACT [21] Appl' 9105402566 Cyan dye-forming phenolic or a-naphtholic coupler Related U.S. Application Data Compounds having p y yy pl ty- [63] Continuation-impart of Scr. No. 213,812, Dec. 29, alkflFarbonamldo Subsnmem m a non'couplmg rmg 97 l abandoned. pos1t1on thereon; a silver halide emulsion containing at least one of such coupler; a color photographic ele- 521 US. Cl. 96/55; 96/74; 96/100 Comprising a PP and at least one Silver 511 1111. C1. G036 7/00; 603C 1/40 ide emulsion Containing the lime coupler applied- [58] Field 6: Search 96/100, 74, 55 hereto; and a method Preparing Cyan PhOwgraphic dye by reacting one of the above defined cou- [56] References Cied plers with oxidized color developing agent.

UNITED STATES PATENTS 41 Claims, No Drawings 2.197,.711 4 1940 Merckx (it al 96/100 1 2 SILVER HALIDE EMULSION CONTAINING emulsion viscosity, adhesion characteristics, or the ACYLAMIDOPHENOL PHOTOGRAPHIC unity of an emulsion layer during modern high-speed COUPLERS multilayer application onto a film backing.

Undesirable changes may also be caused by additives This application is a continuation-in-part of copend- 5 such as wetting agents and color components, and g Patent appli a filed cthese changes can directly affect the coating character- 29, 1971 and now a ndone istics of a photographic emulsion. This problem is sug- This invention relates to a novel group of phenolic g t d, for instance, on page 250 of the text by Zelikand a-naphtholic coupler compounds. More specifiman and L vi, ntitled "Making and Coating Photocally, the present invention relates to a group of new ra hic Emulsi ns; The Focal Press (1964).

color Photographic couplers which are usefully ihcor' including antihalation and gelatin interlayers, up to Poiated into a Photographic element emulsion layer eight or more separate layers may be applied to a film thereof to obtain y y images having increased D base to obtain a modern color photographic element max vahles- (ref. Kirk-Othmer, Vol. 5, pages 8l2845, Encyclope- Coiofed images are customarily obtained in the P dia of Chemical Technology (1950). For this reason g p art y coupling the development Product any induced changes in the physical properties of an -i Oxidized aromatic prim y amino developing emulsion coating may well be as important as coupler agents) with a color-forming or coupling compound in reactivity with oxidized developer. P PoSitioh- The subtractive Process of color forma' The above-listed characteristics are not necessarily tion is ordinarily employed in multicolor photoeie' complete and are often incompatible since the color ihchis and the resulting image y are usually cyan, photographic technology of recent years is complex magenta yeiiow y which are formed in Silver hill and functionally interrelated. In fact, some coupler ide layers Sensitive to complementary iightcharacteristics considered advantageous in earlier pho- A majority of Such coioi' P g p couplers are tographic art may now even be considered undesirable. known and described as foui'eqiiivaieht couplets For the above reasons, it is necessary and desirable which are characterized in requiring the development I to discover new coupler compounds of four light-exposed silver halide molecules in order to h is an object of this invention to obtain a new class ultimately produce one molecule of dye. Also widely of cyan dye formihg couplers inclusive of the and used, are so-called two equi a couplers in which a equivalent type suitable for modern color photographic non-chromophoric coupling-off group is substituted in purposes coupling position. Couplers of this type are functionally It is a further object of this invention to provide new characterized by requiring the development of two excoupler compounds which will readily and efficienfly Posed silver haiidc molecules during development to react with oxidized color developer to obtain cyan dye obtain one molecule of Khcwh two'equivaieht images having substantially improved Dmax values. couplers have coupling-Off groups Such as halo, aikoxy, it is a still further object of this invention to obtain y y y yi 'y i y y or thiocyaho novel photographic elements and photographic emul- S P- substituted in P'P in the case of Phenolic sions utilizing couplers of this invention for color phoor a-naphtholic couplers. Additional couplers of this tographic purposes type are demonstrated, for instance, in US. Pat. Nos. 40 These d other bj fth invention are b i d 3 and 3,227,155- by utilizing a phenolic or a-naphtholic cyan dye- Suitability of an organic compound as a color photof i coupler compound h i a h d S P p s however, depends p more than alkylphenoxy-alkylcarbonamido substituent group subgeneral reactivity. Consideration is also given to the Smuied on a ring position f the phenolic or amaPhco r ba ance. o s grain size and general ptholic nucleus of the coupler. The alkylcarbonamido ness of the dye images obtained. A coupler Should be moiety in the above substituent group is replaced with stable and produce stable photographic dyes having an alkylcarbamyl moiety when the substituent group is precise spectral absorption characteristics when reattached to an a-naphthol coupler ring in the No. 2 poacted with oxidized developer. sition.

Successful color photographic couplers also possess Particularly useful couplers of the invention have the a number of important ancillary characteristics. it is deformulae ALl( ALK l q o I (1) 1-10 O-L-C-NH-Q (II) no I -o-r,..m iz

. or (ALK i ALK sirable, for instance, for a non-diffusible coupler to be h i soluble in minimal amounts of high-boiling coupler 501- m i 0-3; vent in order to obtain thinner and more durable pho- L is a divalent alkylene group, such as an alkylene tographic elements. It is also important that nongroup having 1-20 carbon atoms, including a diffusible couplers be capable of precise incorporation branched chain alkylene group;

into a silver halide emulsion with no adverse effects on ALK is an alkyl group of l-l5 carbon atoms, particu- '3 larlyan alkylgroupof 1-8 carbon atoms, such group including.a branched alkyl such as a secondary or tertiaryalkyl group of 4-8 carbon atoms. and exemplified by methyl, isopropyl, tert. butyl and pentadecyl;

Q is a phenolicor anaphtholic-cyan dye-forming coupler moiety having 1-3 of the above-described p-hydroxy-alylphenoxy-alkylcarbonamido or phydroxy-dialkylphenoxy-alkylcarbonamido' substituent groups attached on a ring position of the phenolic or oz-naphtholic nucleus of the coupler, the alkylcarbonamido moiety of the substituent group being replaced as above with an alkylcarbamyl moiety when the substituent group is attached to an X is defined as (1) hydrogen; (2) a halo group such wherein R is an alkyl group of 1-20 carbons or an aryl group such as a phenyl or a naphthyl group ina-naphtholic coupler in the No. 2 ring position. Suitable dye-forming coupler moieties of the abovedetined types (i.e. Q) are exemplified, for instance in the U.'S. Pat. Nos. 2,275,292;-2,367',531; 2,423,730;

clusive of halo-, alkoxyor alkyl-substituted aryl groups; (8) a thiocyano group; or (9) a heterocyclic radical having a 5-6 membered hererocylic nucleus with at least one nitrogen, oxygen, or sulfur atom, the heterocyclic nucleus being attached to the ring by a bridging -0- or S-- group.

3 2 5 T is (l) a halo group, such as a chloro or'fluoro 3,227,554; group; (2) an alkyl group inclusive of an alkyl "3,458,315 and 3,476,563. t

Illustrative compounds within the scope of the present invention are more specifically described in formugroup of 1-20 carbon atoms'such as methyl, isopropyl and eicosyl; or (3) an alkoxy group inclusive of an alkoxy group of 1-20 carbon atoms such as I methoxy, isopropoxy, or eicosyloxy.

Z is individually defined as in T. 0 ALK R, is l an aryl group such as aphenyl or a naphthyl group exemplified by a fluorophenyl such as p- In in OH 30 fluorophenyl or pentafluorophenyl, as an alkylphenyl such as p-methylphenyl or trifluoro- (ALK) methylphenyl; or (z) -NH-R wherein R, is hyn drogen, an alkyl group of 1-20 carbon atoms, or an aryl group such as a phenyl or a naphthyl group. and Coupler compounds of the invention can be prel mice-R (Iv) V 1- (E n x v 1. r "wli ereini pared, for example, from the corresponding p- L is defined as above,fand is preferably a branched divalent alkylene group oflO-ZO carbon atoms; ALK represents an alkyl group "as defined above;

substituted phenol by nitration'and hydrogenation to obtain an o-amino m-nitro precursor which is then reacted with an acid chloride. A suitable reaction mechan is O-l; 0 nism is described as follows:

H (A) H ratio 7 Q2 2 32504 Pd/C V Y HNO 3 (u) HZSCM.

0 NH (F) NllgR Pd 2 n cl U 1 7 I M1411 g (H) 0 miflR NH IH-C12H25- c H -CH(I!NH wherein X and R are defined as above. tion with an aryl isocyanate to obtain a corresponding Where the o-substituent radical of the coupler moio-ureido substituted intermediate.

ety in formula IV is a ureido group such as a phenyl Compounds within the scope of the present invention ureido, steps (A) through (E)may be followed by reac- 5 are exemplified, for instance, in Tables 1, IA, and II below with reference to formulae V and III.

(III) H z HCO-L-O-QOl1 T Alk TA BLE II C p No. x T z ALK 1 C1- CH3- C1. -C11- (t)C H 2 II C H C1 II 3 n CH O n l n CH3(CH2)6CH2- Cl- (CHzllS n 6 n l8 37 (t)C5 ll n I n y 7 3 c1- -H (1:)c n

8 -0-@ cufl n u s 9 0 11 -0 CH3 )HCl-l -CH3- lq N/ ll 23 l N=N H C1130 n Cul'l The ballasted non-diffusible type cyan couplers of the present invention are usefully incorporated into light-sensitive photographic silver halide emulsion layers and applied onto an emulsion support or film base in a singleor multi-layer color photographic material by known methods (example: the solvent and Fisher fat-tail methods) as described, for instance, in Mannes et al. in U.S. Pat. No. 2,304,939-40 and Jelley et al. in U.S. Pat. No. 2,322,027, in which high-boiling organic solvents are used to dissolve the coupler. Further useful procedures are described, for instance, in Vittum et al. U.S. Pat. No. 2,801,170; Fierke et a1. U.S. Pat. No. 2,801,171 (July 1957); and Julian U.S. Pat. No. 2,479,360 (August 1960), whereby low-boiling or water-soluble organic solvents are used with or in place of a high-boiling solvent. In the case of multi-layer photographic materials or elements, the non-diffusible coupler compounds are generally incorporated into the red-sensitive silver halide emulsion layer and preferably utilize minimal amounts of high-boiling solvents.

Generally speaking, a useful coupler concentration will vary from about -200 mg/ft of coated material, a range of -50 mg/ft being generally satisfactory for use in photographic paper, with overlapping and higher concentrations found useful in color photographic films.

A variety of color coupler-containing photographic materials and elements are obtainable utilizing the above family of cyan dye-producing couplers. Generally speaking, however, such photographic materials and elements will comprise the following main components:

(A) A support layer such as cellulose nitrate film, cellulose acetate film, polyvinylacetal film, polystyrene film, poly (ethylene terephthalate) film, polyethylene film, polypropylene film and related films of resinous materials as well as paper, polyethylene coated paper, glass, and others.

(B) An antihalation layer such as a dye-containing gelatin, starch, etc., as described, for instance, in Glafkides Photographic Chemistry, Volume 1, pages 470-471, Arrowsmith Ltd. 1958;

(C) One or more, preferably three light-sensitive and differently-sensitized color coupler-containing silver halide emulsion layers coated onto the support, optionally with one or more gelatin spacer layers between. The support is conveniently coated in succession with a red-sensitive layer containing one or more of the above-defined class of cyan-dye-producing coupler, a green-sensitive layer and a blue-sensitive layer, either with or without a Carey-Lea filter layer between the blueand greensensitive layers. The three differently color-sensitized layers can also be arranged in any other order over one another that is desirable, with the exception that a Carey-Lea filter layer cannot be placed over a blue-sensitive layer.

The light-sensitive silver halide emulsions can include coarse, regular, or fine grain silver halide crystals or mixtures thereof such as silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide and mixtures thereof; such emulsions are described, for instance, in The Photographic Journal, Volume LXXlX, May 1939, pages 330-338; Journal of Photographic Science, Volume 12, No. 5, Sept/Oct 1964, pages 242-251, and also in U.S. Pat. Nos. 2,184,013; 2,456,953; 2,541,472; 2,563,785; 3,367,778 and 3,501,307. Such silver halide emulsions typically are gelatin emulsions although other hydrophilic colloids can be used in accordance with usual practice.

(D) One or more gelatin or hydrophilic spacer layers between the light-sensitive emulsion layers or the emulsion layers and Carey-Lea filter layer as above described; and

(E) A protective water-permeable overcoat layer,

such as gelatin or other hydrophilic colloids; The overish Pat. No. 623,448, and other ingredients such as i buffering agents (e.g., an acidic or basic material), and

ultra-violet light absorbers such as 2,2 -di-hydroxy 4,4'-dimethoxybenzophenone, 4,4-dimethoxyben- ,izophenone, 4 ,4-di,azidostilbene-2,2'-disulfonic acid sodium salt, and sodium (a-phenylhydrazone.

In addition, photographic materials and elements utilizing the present cyan-dye-forming couplers can usefully contain brighteners such as stilbenes, triazines, oxazoles and coumarins as described, for instance, in German Pat. Nos. 972,067; 115,024; and in U.S. Pat. No. 2,933,390; they may also contain spectral sensitizing dyes to impart additional sensitivity to light-sensitive silver halide emulsion layers.

This invention is further described, although not limited, by the following examples. Examples V-Vll include couplers not of the invention for purposes of comparison.

EXAMPLE I -Acylamido-acylamido-5 -aminophenol A solution of 0.1 mole of 2-amino-5-nitrophenol and 0.2 mole of quinoline in 300 ml of dioxane is admixed with a solution of 0.1 mole of acid chloride in 50 ml of dioxane. The resulting reaction mixture is stirred at room temperature for 1 hour, then poured into 1 liter of ice water containing 10-15 ml of concentrated hydrochloric acid. The solid product then is collected, washed with water and recrystallized from aqueous ethanol solvent. .05 Mole 2-acylamido-5-nitrophenol intermediate product is dissolved into 200 ml of dioxane containing a teaspoonful of palladium-on-charcoal. This mixture is then placed in a Parr bottle and reduced under hydrogen (40 psi) at 40C. After about 30 min. the reaction mixture is filtered; a solution of the 2- acylamido-S-amino product (ref. pg. 6 intermediate G) can be used directly for preparation of desired couplers.

EXAMPLE ll Coupler 2 of Table l 200 Ml of a dioxane containing 11.4 g (0.05 mole) of 2-benzamido-S-aminophenol prepared by the general procedure described above on page 6 and in Example 1 is admixed with 13 g (0.1 mole) of quinoline and 22.7 g (0.05 mole) of (3-tert-butyl-4-acetoxyphenoxy) tetradecanolyl chloride. The mixture is stirred at room temperature for 2' hours, then poured onto 500 ml of ice-water containing 10-15 ml of concentrated HCl. The resulting resinous solid is then collected, triturated with petroleum ether and recrystallized from cyclohexane; (m.p. l 19-120C). The above acetoxy intermediate is then dissolved in 200 ml of ethanol and treated with 50 ml of 2 percent alcoholic potassium hydroxide. After stirring for 0.5 hour, the mixture is pured onto 500 ml of ice-water and then acidified with concentrated hydrochloric acid. The resulting viscous oil is separated out, and triturated with petroleum ether until it solidifies. Upon recrystallization from CHCl petroleum ether there is obtained a product identified as coupler No. 2 (m.p. l33-l35C).

EXAMPLE Ill Couplers l, 3 and 4 of Table I Couplersl, 3 .and 4 are prepared asin Example 11 from' i the corresponding 2-(4-fluoro-benz amido)-5- aminophenol, i g aminophen'ol, andZ-pentafluorobenzainido-4 flu oro-5- 17 aminophenol respectively. The couplers have melting points of 84-86, l47-149, and 118l19C.

EXAMPLE IV Coupler l of Table ll To a solution of 5.8 g (0.03 mole) of 2-amino-4,6- dichloro-S-methyl phenol in 500 ml of acetic acid is added with stirring 2.5 g of sodium acetate and 13.6 g (0.03 mole) of (3-tert-butyl-4-acetoxyphenoxy) tetradecanoyl chloride. The mixture is stirred for 1 hour, poured onto 1 liter of ice-water, and the resulting gummy solid collected and dissolved in diethyl ether. After drying over Na SO the diethyl ether solvent is removed under reduced pressure and triturated with petroleum ether until it solidifies. The solid obtained is then dissolved in 300ml of ethanol and treated with 50ml of 2 percent alcoholic potassium hydroxide. After stirring under a blanket of nitrogen for 0.5 hour, the mixture is drowned in ice-water and strongly acidified with HCl. The resulting gelatinous solid is collected,

triturated with petroleum ether, and recrystallized from acetonitrile to obtain 8.5 g of product having a m.p. of 8 l82C.

EXAMPLE V Related Couplers For Comparison, See Table Ill V on I I H Na-co-R 12 420-11 TABLE III Compound No. I R2 R11 1 I #1 0 -Cli- Q}? a n "a c o-cna c 12 c 11 1 -Q o-ca- Q-er H a -t 4 9 F IV olcn- F F I c a c a F r F F F v a c oc.1

4 9 F s n F TABLE III Continued Compound No. R 2 l v1 0cm F F F L I F c n 12 I and as VII H -t Cl NIICOCH C H CH 2% t EXAMPLE VI -Continued Twenty-four photographic test film strips respectively as 1A, 1B 58, IA, 18 VIIB, are prepared color Developing Solution B by coating a transparent cellulose acetate support with light-sensitive gelatinous silver bromo-iodide emulsion 'g 'i gg 'ggatg fifimgtf fir coating to obtain 136 mg silver/ft 450 mg gelatin/H Sumue hydrate y Sq 5.0 g

and 78 mg/ft of one of coupler 1-5 and l-Vll, and A 50% NaBr Solution and B strips containing equal molar amounts of the (PH 1015) I same coupler dissolved into 39 mg/ft of dl-n-butyl phthalate with B-ethoxy ethyl acetate as auxiliary solvent then dispersed into an aqueous gelatin solution, Light Fading Tests etc., in the manner described, for instance, in Example l'of U.S. Pat. No. 2,949,360. The ratio of coupler sol- 40 The extent to l mage a under the vent coupler for this purpose is U/L The Coated influence ofllght 1S determined by sub ect ng processed strips are sensitometrically exposed through a graduatcoatmgs to a i q zl'day Skyhght B ed-density test object and processed in the usual man- (SANSAamj f the l sf decrease In dye ner at 20C., one duplicate being treated with Color density m an area havmg 2 f densltx 9 Developing Solutions A and B, as hereinafter deg g g l rlesultmg Lght Fade scribed. The strips are then stop-fixed, washed, silver as i y l t d l bleached, washed, fixed, washed, stabilized and dried e o w .unreac e P i' causes.-

in the usual manner thereafter tested as explained wanted stain under the influence of light ls determined by exposing processed coatings to SANS, as above delow, and evaluated to determine their maximum Image d d Sit and ht and heat fadin characteristics scribed, and recording the resulting increase in density t f in Tabl IV g to blue light (420 nm) in a D min area of the coating. 6 es s e or e This increase is termed PrintOut (PO) and is recorded in terms of percent density increase.

Color Developing Solution A Heat Fadmg Tests O 800 I The extent to which the image dyes fade under the sgdium hexamcta phnsphutc 05 influence of heat and humidity is determined by sub- Na sq, 2.0 g jecting coatings to a temperature of C at a relative 'QT IQ'S B' f Z 2 0 g humidity of 70 percent for 1 week. The resulting de- Main3 20 g 60 crease in image dye density is termed Heat Fade" NaBr Solution 1 F" (H.F.) and is measured in terms of decrease in dye dento (PH 1086) sity in density units.

The effect of heat on unreacted coupler is deter- Developmg B mined by subjecting coatings to the above heat and hu- H20 800 ml midity conditions, and determining the increase in den- Ben zyl alcohol 4.0 ml sity (i.e. yellowing) in a D min area (420 nm) of the glz gl Phosphate 18 g coating, and recording this in terms of per cent density 40% NaOH solution' 0.4 ml increase.

TABLE IV Coupler Coupler No. Dev. D,,,,,, A LF 7( Po HF 7r Yell. M.P. C.

B 3.19 651 0.07 1 +0.03 9 2 A 2.85 662 0.08 l 0 3 133-135 B 3.48 651 0.06 1 +0.10 7 l A 2.74 663 0.14 1 +0.03 6 166-167 B 2.00 657 0.12 0 0 1 111 A 2.81 662 0.07 l 0 3 184-185 B 2.30 652 0.12 0 0 4 IV A 3.20 654 0.08 0 +0.03 5 133-134 B 2.90 664 0.07 0 +0.02 5 V A 3.40 669 0.09 2 +0.02 7 194-195 B 3.22 654 0.08 3 +0.02 8 VI A 3.80 661 0.10 2 +0.03 7 112-113 B 3.15 646 0.07 2 +0.03 7 VII A 3.45 664 0.03 0.5 +0.06 5 l22l23 Based on the above data, it is apparent that a substantially higher D value is obtained when using the coupler compounds of the present invention (Arabic number) with analogous compounds outside of the present invention (Roman numerals) without substantial disadvantage with respect to other important coupler characteristics.

EXAMPLE VII Couplers l-4 of the invention have D cyan dye image values which are photographically satisfactory and possess the additional advantages associated with systems having no retained high boiling coupler solvent (i.e. increased durability and better image resolution).

This invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected with the spirit and scope of the invention.

We claim:

1. A photographic silver halide emulsion containing as color photographic coupler a phenolic cyan dyeforming coupler compound having a p-hydroxy-malkylphenoxyalkylcarbonamido group substituted on a non-coupling ring position of the phenolic nucleus of the coupler.

TABLE V Coupler Coupler No. Dev. A LF 7: HF 71 Yell. M.P. C.

B 2.03 657 0.12 7 +0.05 10 l A .98 665 0.25 3 +0.05 6 166-167 B 1.49 651 0.30 4 +0.06 7 ll A .56 No values recorded -156 B .85 No values recorded B 1.06 650 0.15 0 0.02 2 VII A 1.48 668 0.22 5 +0.07 7 194-195 at least one color photographic coupler having the formula ALK 5 NllCO-R (ALK) 20 wherein m is -3;

L is a divalent alkylene group;

ALK is an alkyl group of l-l carbon atoms;

X is (1) hydrogen, (2) a halo group, (3) an aryloxy group, (4) a thioaryl group, (5) an alkoxy group, (6) a thioalkyl group, (7) a thiocyano group, (8) a heterocyclic radical having a 5-6 membered heterocyclic nucleus with at least one nitrogen, oxygen, or sulfur atom, said heterocyclic nucleus being attached to the ring by a bridging O or S group, or (9) an acyloxy group of the formula R COO wherein R is an alkyl group of 1-29 carbon atoms or an aryl group;

T is (l) a halo group, (2) an alkyl group or (3) an alkoxy group;

Z is individually defined as in T; and

R is(1) an aryl group of(2) Nl-lR in which R is hydrogen, an alkyl group of lcarbon atoms 40 or an aryl group.

3. A photographic silver halide emulsion containing color photographic coupler having the formula OH ALK l z NllCO-LO OH ALK T it wherein n is 0-1 L is a divalent alkylene group of 10-20 carbon atoms;

ALK is an alkyl group of l-8 carbon atoms;

X is (1) hydrogen, (2) a halo group, (3) an alkoxy group, (4) an arylthio group, (5) a thiocyano group, (6) a heterocyclic radical having a 5-6 membered heterocyclic nucleus with at least one nitrogen, oxygen, or sulfur atom, said heterocyclic nucleus being attached to the ring by a bridging O or S group or (7) an acyloxy group of the formula R CO-O wherein R is an alkyl group of l-2O carbon atoms or an aryl group;

T is (l) a halo group, (2) an alkyl group or (3) an alkoxy group; and

Z is individually defined as in T. 4. A photographic silver halide emulsion of claim 2 wherein L is a divalent branched alkylene group of lO-2O carbon atoms; X is hydrogen or a halo group; T is an alkoxy group of l-20 carbon atoms; and Z is individually defined as an alkyl group, an alkoxy group or a halo group. 5. A photographic silver halide emulsion of claim 2 wherein L is a divalent branched alkylene group of lO-20 carbon atoms; X is a hydrogen or a halo group; T is an alkyl group, an alkoxy group or a halo group;

and Z is an alkoxy group of l-20 carbon atoms. 6. A photographic silver halide emulsion of claim 2 wherein ALK is a tertiary alkyl group of 4-8 carbon atoms. 7. A photographic silver halide emulsion containing a color photographic coupler having the formula NHCO-R l -CONH X is hydrogen, fluoro, or chloro; and R' is a substituent of the formulae HO 0(|3H q C ll 25 9. A photographic silver halide emulsion of claim 7 wherein R', is p-fluorophenyl; and R' is ol{ -Cli- I C l' 25 15. A photographic silver halide emulsion of claim 7 wherein l I 11 X IS fluoro;

R' is phenylamino; and 10. A photographic silver halide emulsion of claim 7 R' is wherein R s phenyl; and 5 OH R 2 IS l 12*25 OH O-CH 0 CuH9( 16. A photographic silver halide emulsion of claim 7 wherein l 7 X is chloro; ll. photographic silver halide emulsion of c arm is p y and wherein R" is p-trifluoromethyl phenyl; and 2 R g is OH 0-Cli- I OH 0- l-l- I l2 25 c H (t) C H (t) 9 17. A silver halide emulsion containing 4,6-dichloro- 5-methyl-2[a(p-hydroxy-m-tert. butylphenoxy)- 12. A photographic s|lver halide emulsion of claim '7 tridecylcarbonamido]pheno] whefm 18. A silver halide emulsion containing 4-fluoro-5[aa halo group; (p-hydroxy-m-tert. butylphenoxy)tridecylcarbonamidpentafluol'o Phenyli and 40 o]-2(pentafluorophenyl carbonamido)-phenol. R 2 19. A color photographic element comprising a photographic silver halide emulsion layer containing as a Oil O-CH- cyan dye-forming coupler a phenolic cyan dye-forming coupler compound having a p-hydroxy-alkylphenoxy- C ll alkylcarbonamido group, or a p-hydroxy-dialkylphenoxy-alkylcarbonamido substituent group substi- (t) tuted on a non-coupling ring position of the phenolic i g nucleus of the coupler.

20. A color photographic element comprising a support and at least one photographic silver halide emulsion applied thereto containing a cyan dye-forming coupler of the formula 13. A photographic silver halide emulsion of claim 7 wherein X is hydrogen R" is phenylamino; and

R 2 IS ALK 0H OCH" Ol-l 25 Z NHCO-L-O on 01 H (t) 14. A photographic silver halide emulsion of claim 7 X wherein X is hydrogen; R, is 2,4-dichlorophenylamino; and R: is or OH ALK NHCO-R H -O-LCQNH (ALK) x wherein n is 0-1;

L is a divalent alkylene group;

ALK is an alkyl group of 1-15 carbon atoms;

X is (l) hydroge, (2) a halo group, (3) an aryloxy group, (4) a thioaryl group, (5) an alkoxy group, (6) a thioalkyl group, (7) a thiocyano group, (8) a heterocyclic radical having a 5-6 membered heterocyclic nucleus with at least one nitrogen, oxygen, or sulfur atom, said heterocyclic nucleus being attached to the ring by a bridging O- or -S group, or (9) an acyloxy group of the formula R -COO wherein R is an alkyl group of l-20 carbon atoms or an aryl group;

T is (l) a halo group, (2) an alkyl group or (3) an alkoxy group;

Z is individually defined as in T; and

R is (1) an aryl group or (2) -Nl-lR in which R is hydrogen, an alkyl group of l-20 carbon atoms or an aryl group.

21. A color photographic element comprising a support and at least one photographic silver halide emulsion applied thereto containing a cyan dye-forming coupler of the formula ALK . -O- or',S. group or (7:) an acyloxy group of the formula R -COO wherein R is an alkyl group of l-20 carbon'atoms or an aryl group; T is (l) a halo group, (2) an alkyl group or (3) an alkoxy group; and Z is individually defined as in T. 22. A color photographic element of claim 20 wherein L is a divalent branched alkylene group of lO-2O carbon atoms; X is hydrogen or a halo group; T is an alkoxy group of l-20 carbon atoms; and Z is individually defined as an alkyl group, an alkoxy group, or a halo group. 23. A color photographic element of claim 20 wherein L is a divalent branched alkylene group of 10-20 carbon atoms; X is a hydrogen or a halo group; T is an alkyl group, an alkoxy group or a halo group;

and Z is an alkoxy group of l-2 0 carbon atoms. 24. A color photographic element of claim 20 wherein ALK is a tertiary alkyl group of 4-8 carbon atoms. 25. A color photographic element comprising a support and at least one photographic silver halide emulsion applied thereto containing a cyan dye-forming coupler of the formulae I NllLO-R R2-CONH ora HO -OCl-l or c 1-1 L12H25 C ll flz) 27. A color photographic element of claim 25 wherein R, is p-fluorophenyl; and R, is

no I o-caclzuzs t c r- J 28. A color photographic element of claim 25 wherein R, is phenyl; and R is 1.10 O-CH- I 12325 c Hgi 29. A color photographic element of claim 25 0 wherein R, is p-trifluoromethyl phenyl; and R, is

30. A color photographic element of claim 25 wherein X is a halo group; R, is pentafluoro phenyl; and R is Oll O-CH- (t) C H 31. A color photographic element of claim 25 wherein X is'hydrogen R, isphenylamino; and R g is HO -O-CH I C d-I (t2) C1iH 32. A color photographic element of claim 25 wherein X is hydrogen R, is 2,4-dichlorophenylamino; and

33. A color photographic element of claim 25 wherein X is fluoro;

R, is phenylamino; and

R, is

Cql-l 34. A color photographic element of claim 25 wherein X is chloro; R, is phenylamino; and R is H0 o-cn- Cull phenyl- 31 32 38, A color photographic element comprising a 110. 41. A photographic silver halide emulsion as in claim tographic silver halide emulsion layer containing S-[a- 8 (p-hydroxy-m-(t)-butylphenoxy)-tridecylcarv herein bonamido1-2-(phenyl) phenol. X is chloro,

39. A color photographic element comprising a pho- 5 '1 i8 phlor phenyl, and tographic silver halide emulsion layer containing S-[a- 2 is (p-hydroxy-m-(t)-butylphenoxytridecylcarbonamido[-2-( p-fluoromethyl phenyl phenol. I O CH 40. A method for preparing a cyan photographic dye 10 I comprising contacting a phenolic coupler compound 1-1 having a p-hydroXyphenoxy-m-alkyl carbonamido substituent in a non-coupling ring position with oxidized C H9 color developing agent during development of an im- 4 agewise exposed silver halide emulsion containing said coupler.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,880,661 DATED April 29, 1975 INVENTOR(S) Philip T. Lau, Ilmari F. Salminen and Leo E.

I Beavers r It rs certrfred that error appears In the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, line 8, "alylphenoxy" should read -alkyl phenoxy---;

Column 16, line 19, delete the second occurrence of "acylamido" and insert 2- before the first occurrence oi "acylamido";

Column 23, line 33, (claim 2) "R should read -R and same line, "1-29" should read 1-20 Column 27, line 17, (claim 20) "hydroge" should read --hydrogen--;

Column 30, line 30, (claim 33) "R' should read --R' Signed and Sealed this twenty-fourth Day Of February 1976 [SEAL] A tres t:

C. MARSHALL DANN RUTH C. MASON Commissioner of Parents and Trademarks Arresting Officer 

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING AS COLOR PHOTOGRAPHIC COUPLER A PHENOLIC CYAN DYE-FORMING COUPLER COMPOUND HAVING A P-HYDROXY-MALKYLPHENOXYALKYLCARBONAMIDO GROUP SUBSTITUTED ON A NONCOUPLING RING POSITION OF THE PHENOLIC NUCLEUS OF THE COUPLER
 2. A photographic silver halide emulsion containing at least one color photographic coupler having the formula
 3. A photographic silver halide emulsion containing a color photographic coupler having the formula
 4. A photographic silver halide emulsion of claim 2 wherein L is a divalent branched alkylene group of 10-20 carbon atoms; X is hydrogen or a halo group; T is an alkoxy group of 1-20 carbon atoms; and Z is individually defined as an alkyl group, an alkoxy group or a halo group.
 5. A photographic silver halide emulsion of claim 2 wherein L is a divalent branched alkylene group of 10-20 carbon atoms; X is a hydrogen or a halo group; T is an alkyl group, an alkoxy group or a halo group; and Z is an alkoxy group of 1-20 carbon atoms.
 6. A photographic silver halide emulsion of claim 2 wherein ALK is a tertiary alkyl group of 4-8 carbon atoms.
 7. A photographic silver halide emulsion containing a color photographic coupler having the formula
 8. A photographic silver halide emulsion of claim 7 wherein R''1 is phenyl, p-fluorophenyl, pentafluorophenyl, trifluoromethylphenyl, phenyl amino, or alkylamino of 1-15 carbon atoms; X'' is hydrogen, fluoro, or chloro; and R''2 is a substituent of the formulae
 9. A photographic silver halide emulsion of claim 7 wherein R''1 is p-fluorophenyl; and R''2 is
 10. A photographic silver halide emulsion of claim 7 wherein R''1 is phenyl; and R''2 is
 11. A photographic silver halide emulsion of claim 7 wherein R''1 is p-trifluoromethyl phenyl; and R''2 is
 12. A photographic silver halide emulsion of claim 7 wherein X'' is a halo group; R''1 is pentafluoro phenyl; and R''2 is
 13. A photographic silver halide emulsion of claim 7 wherein X'' is hydrogen R''1 is phenylamino; and R''2 is
 14. A photographic silver halide emulsion of claim 7 wherein X'' is hydrogen; R''1 is 2,4-dichlorophenylamino; and R''2 is
 15. A photographic silver halide emulsion of claim 7 wherein X'' is fluoro; R''1 is phenylamino; and R''2 is
 16. A photographic silver halide emulsion of claim 7 wherein X'' is chloro; R''1 is phenylamino; and R''2 is
 17. A silver halide emulsion containing 4,6-dichloro-5-methyl-2( Alpha (p-hydroxy-m-tert. butylphenoxy)tridecylcarbonamido)phenol.
 18. A silver halide emulsion containing 4-fluoro-5( Alpha -(p-hydroxy-m-tert. butylphenoxy)tridecylcarbonamido)-2-(pentafluorophenyl carbonamido)-phenol.
 19. A color photographic element comprising a photographic silver halide emulsion layer containing as a cyan dye-forming coupler a phenolic cyan dye-forming coupler compound having a p-hydroxy-alkylphenoxy-alkylcarbonamido group, or a p-hydroxy-dialkylphenoxy-alkylcarbonamido substituent group substituted on a non-coupling ring position of the phenolic nucleus of the coupler.
 20. A color photographic element comprising a support and at least one photographic silver halide emulsion applied thereto containing a cyan dye-forming coupler of the formula
 21. A color photographic element comprising a support and at least one photographic silver halide emulsion applied thereto containing a cyan dye-forming coupler of the formula
 22. A color photographic element of claim 20 wherein L is a divalent branched alkylene group of 10-20 carbon atoms; X is hydrogen or a halo group; T is an alkoxy group of 1-20 carbon atoms; and Z is individually defined as an alkyl group, an alkoxy group, or a halo group.
 23. A color photographic element of claim 20 wherein L is a divalent branched alkylene group of 10-20 carbon atoms; X is a hydrogen or a halo group; T is an alkyl group, an alkoxy group or a halo group; and Z is an alkoxy group of 1-20 carbon atoms.
 24. A color photographic element of claim 20 wherein ALK is a tertiary alkyl group of 4-8 carbon atoms.
 25. A color photographic element comprising a support and at least one photographic silver halide emulsion applied thereto containing a cyan dye-forming coupler of the formulae
 26. A color photographic element of claim 25 wherein R''1 is phenyl, p-fluorophenyl, pentafluorophenyl, trifluoromethylphenyl, phenyl amino, or alkylamino of 1-15 carbon atoms; X'' is hydrogen, fluoro, or chloro; and R''2 is a substituent of the formulae
 27. A color photographic element of claim 25 wherein R''1 is p-fluorophenyl; and R''2 is
 28. A color photographic element of claim 25 wherein R''1 is phenyl; and R''2 is
 29. A color photographic element of claim 25 wherein R''1 is p-trifluoromethyl phenyl; and R''2 is
 30. A color photographic element of claim 25 wherein X'' is a halo group; R''1 is pentafluoro phenyl; and R''2 is
 31. A color photographic element of claim 25 wherein X'' is hydrogen R''1 is phenylamino; and R''2 is
 32. A color photographic element of claim 25 wherein X'' is hydrogen R''1 is 2,4-dichlorophenylamino; and R''2 is
 33. A color photographic element of claim 25 wherein X'' is fluoro; R''2 is phenylamino; and R''2 is
 34. A color photographic element of claim 25 wherein X'' is chloro; R''1 is phenylamino; and R''2 is
 35. A color photographic element comprising a photographic silver halide emulsion layer containing 4,6-dichloro-5-methyl-2( Alpha -(p-hydroxy-m-tert. butylphenoxy) tridEcylcarbonamido) phenol as a cyan dye-forming coupler.
 36. A color photographic element comprising a support, at least one photographic silver halide emulsion and 4-fluoro-5( Alpha -(p-hydroxy-m-tert. butylphenoxy) tridecylcarbonamido)2-(pentafluorophenyl carbonamido)-phenol as a cyan dye-forming coupler.
 37. A color photographic element comprising a photographic silver halide emulsion layer conatining 5-( Alpha -(p-hydroxy-m-(t)-butylphenoxy-tridecylcarbonamido)-2-(p-trifluoromethyl phenyl-carbonamido)phenol.
 38. A color photographic element comprising a photographic silver halide emulsion layer containing 5-( Alpha -(p-hydroxy-m-(t)-butylphenoxy)-tridecylcarbonamido)-2-(phenyl) phenol.
 39. A color photographic element comprising a photographic silver halide emulsion layer containing 5-( Alpha -(p-hydroxy-m-(t)-butylphenoxy-tridecylcarbonamido(-2-(p-fluoromethyl phenyl)-phenol.
 40. A method for preparing a cyan photographic dye comprising contacting a phenolic coupler compound having a p-hydroxyphenoxy-m-alkyl carbonamido substituent in a non-coupling ring position with oxidized color developing agent during development of an imagewise exposed silver halide emulsion containing said coupler.
 41. A photographic silver halide emulsion as in claim 8 wherein X is chloro, R''1 is p-chlorophenyl, and R2 is 